Treatment of textiles with acetylene diurea derivatives



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UnitedStates PatentO TREATMENT OF TEXTILES WITH ACETYLENE DIUREA DERIVATIVES Dmitry M. Gagarine and Henry Repokis, Danville, Va.,

assignors to Dan River Mills, Incorporated, a corporation of Virginia No Drawing. Application February 29, 1952, Serial No. 274,310

Claims. (Cl. 117--139.4)

The present invention relates to the treatment of cellulosic fabrics with aqueous solutions of heat hardening resin forming materials and acid liberating catalysts to provide improved crease angle recovery, dimensional stability and other desirable properties with a minimized concomitant decrease in wear life of the treated fabric. More particularly the invention relates to improving the effectiveness or efiiciency of acetylene diurea methylols and methylol ethers by proper neutralization of fabrics and the use of catalysts, hereinafter referred to as quaternary ammonium catalyst having the general formula:

wherein R is an aliphatic radical having from 14 to 22 carbon atoms, P is a pyridinium or lower aliphatic substituted pyridinium group, X is the anion of a strong acid and A is a connecting linkage selected from the group consisting of an amide, an ester, and an ether.

Treatment of fabrics with compounds falling inthe class of acetylene diurea methylols and methylol ethers is shown in German Patent No. 702,146. However, commercially feasible methods heretofore used in applying these compounds have not produced results substantially better than those obtained with other and more universally used resin; forming materials such as urea formaldehyde and melamine formaldehyde.

The normal steps of treating textile fabrics with resin forming materials to produce crease-anglerecovery are:

3. Curing the resin forming material on the thus "dried impregnated fabric.

Productionof fabrics having ahigh degree of creaseangle recovery has been limited in the past to fabricshaving sufiicient initial strength to permit a considerable reduction in tear strength of the treated fabrics without bringing the tear strength to the dangerpoint. In other words, all prior processes capable of producing satisfactory crease-angle recovery also produced a concomitant decrease in tear strength and, accordingly, it has been generally necessary to choose a fabric which will be strong enough for normal wear even after a major reduction intear strength.

The tear strength of fabrics treated in accordance with the present invention is reduced much less, thus permitting the selection of sheer fabrics having a low initial tear strength before treatment to produce crease-angle re covery.

According tothe present invention the general steps of treating the fabrics are the same as those outlined above. It has now been found that the beneficialresults of a invention.

2,724,664 Patented Nov. 22, 1955 2 reduction in tear strength for any given degree of crease angle recovery can be obtained by the combination:

The neutralization of the fabric can be accomplished in any one of several ways, the critical factor being the requirement that substantially all .sodium ions on the fabric be neutralized. A satisfactory. neutralization test is to titrate the amount of sodium ions on the fabric as sodium hydroxide. When the thus tested sodium hydroxide is less than .01 the fabric is sufficiently neutral. One method of neutralizing the fabric consists in washing the fabric in a mild acid solution and rinsing the acid treated fabric with water having a pH of less than 7.

Another method of neutralizing the fabric is the use of a low molecular weight acid releasing material in the fabric treating bath which is capable of easily penetrating cellulosic fibers and which releases acid during the heating of the fabric to neutralize sodium ions in situ. It is important that the amount of acid releasing material used for neutralization be less than that causing catalytic action inasmuch as premature catalysis will. produce low tear strengths which are avoided by proper use of the present It has now been found that about 1.1 to 1.5 molsof acid releasing material will neutralize 1 mol of alkali to produce optimum results of neutralization without catalysis. Suitable acid releasing materials for sodium ion neutralization are 2,2 methyl amino propanol hydro.- chloride, monoethanol amine hydrochloride, diethanol amine hydrochloride, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium chloride, and a sulfur dioxide-formaldehyde complex.

It has now been found that quaternary ammonium catalysts having the formula:

i ii l wherein R is an aliphatic radical having from 14 to '22 carbon atoms; P is a pyridinium or lower aliphatic substituted pyridinium group, X isthe anion of a strong acid and A is a connecting linkage selected from the group consisting of an amide, an ester, and an ether, will release acid only in the curing step and that these catalysts produce particularly beneficial results with the hereinafter defined acetylene diurea derivatives. These catalysts are known to be generally equivalent to other acid catalysts for otherresin forming materials, such as urea formaldehyde and melamine formaldehyde, but the unexpected result obtained by using these catalysts with acetylene diurea derivatives does not extend to use of these catalysts with other resin forming materials such as urea formaldehyde and melamine formaldehyde.

The gist of the present inventionis the discovery that the above defined quaternary ammonium catalysts have a marked superiority over conventional catalysts when used to catalyze the reaction of acetylene diurea derivatives with neutralized cellulose, which marked superiority is not present with other resin forming materials normally used in the treatment of textile fabrics for the production of crease-angle recovery.

Catalytic compounds which have been tested and 3 .I provento be generallysatisfactory for purposes .of this. invention are:

Stearamido methyl; pyridinium. chloride.

stefi famidolmethyl pyridinium nitrate.

Stearamido methyl beta picolinium chloride.

Stearamido methyl beta picolinium nitrate.

Octadecyl oxymethyl pyridinium chloride.

Octadecyl oxym'ethy'l pyridinium nitrate.

Octadecyl oxym ethyl pyridinium beta picolinium chloride.

Octadecyl oxymethyl pyridinium" beta picolinium nitrate.

Octadecyl oxymcthyl 2 ethyl 5 methyl-pyridinium chloride."

Stearoyl oxymethyl pyridinium chloride.

Palmatiamido methyl pyridinium chloride.

Hexodecyl' oxymethyl pyridinium. chloride.

Stearamido methyl gamma picolinium chlorides:

Stearamidomethyl gamma picolinium nitrate.

Stearamido methyl beta: .gamma' picolin'ium chloride.

Stearamido :methyl beta 'gamma picolinium nitrate.

A preferred catalyst falling into the generic grouping heretofore referred to as quaternary ammonium" cataly'sts is of undetermined composition." It is believed to contain stearamido methyl pyridinium nitrate as one component and it is known that methylolgroups are present in some component 'of the composition; The'preferred catalyst, hereinafterreferred to as a stearamido methyl EXAMPLE ,A

Preparation of stearamidb methyl pyridinium-nitrate composition 413 lbs. of .stearamidetArmid HT. sold by.Armour& Co.) and 103 lbs. paraformaldehydeare added with stirriugto 196 lbs. of perchorethylene. (a substantially inert solvent for purposes of this. invention) held at .160. F. The paraformaldehyde andstearamide are reacted at 210 pyridinium nitrate composition, is prepared as follows: -1

F. for one hour after which 133 lbs. of pyridine nitrate are added. The reaction continues at 210 F. for- 30 minutes. The mixture. is stirred throughout. the reaction.

The pyridine nitrateusedin this reaction is anapproximately 88% pure product-containing excess pyridine to' I the extent that a 10% solutionofi it hasa pHlof about 4.35. It has been found that if lbs. of fuming, HNOs are slowly added to 77 lbs. of pyridine with cooling and stirring, a satisfactory pyridine nitrate can be produced.

The reaction product of 'parafor'maldehyde, stearamide,

and pyridinium nitrate is artificially slowly cooled and solvents are added to form the finished product as follows: When thesreaction mass reached 198 F.add 77 lbs.

butanol I Whenthe reaction mass reaches 176 F.-add 33 lbs. isopropanol. Whenthereactionmass reaches 150 methanol. The product is light tan paste atroom temperature and tends to stiffen: to a solid at lower temperature. It -is water dispersable in warm water for immediate use as a catalyst.

The term acetylene diurea derivatives as used in this specification includes those methylols and methylol ethersofacetylene vdiureawhich arewater soluble and-.re-

active with cellulose. Typical. compounds which have been testcdand .found generally satisfactory are:

Dimethylol acetylene diurea;

' Tetramethylol acetylene diurea dimethylol.

Themethylol acetylene diurea. resinous products may be prepared in two steps, the first of which comprises 4 producing..the..acetylenc..diurea.by. reacting glyoxal with urea in an acid medium, and then producing the methylol thereof by reacting the acetylene diurea with formaldehyde in a basic medium and finally condensing or polymerizing the reaction product in.an acid medium. Along with the trimethylol acetylene'diurea, some dimethylol acetylene diureamay bevformedzwithout disadvantage.

The formaldehyde which' is reacted with acetylene diurea may bein the formof Formalin or as paraformaldehyde.

Illustrative but non-limiting examples ofthe preparation of some preferred acetylene diurea derivatives on a pilot plant scale is as 'follows'rz EXAMPLE B Preparation of acetylene diurea Glyoxal 30.3% .solution .'.1680lbs;+-lmol Urea 1806i lbs,.3.4 mols. Hydrochloric acidsolution (28% I HCl by weight.) ISO-lbs.

Place the glyoxal in a stainlesssteel'reaction kettle equipped with stirrer, steam coils; cooling jacketand a thermometer; Add the urea while stirring constantly. Much of the-urea remains'undissolved; but sufficient'dos dissolve to cause the tempcrature-to'fall as lowas'40*F.

Noiv'add the hydrochl'orlieacid, "which bringsthe'pl-I to between *1 and? Start heating themixturebymieans of the steam coil. As the .mixture heats, an exothermic reaction starts. At about F. a granular White precipitate forms. When the temperature reaches F. the reaction is well underway, and the heating is discontinued. If left alone at this stage, the reaction mixture continues to heat up-and-firially boils and 'foa'ms violently. Accordingly, the temperature is allowed to rise to'200 F. and-then the mixtureis cooled by means of thecoolingjacketto l95" "-F.'- It is kept at this "temperature-of'-l95200 F. for-ten-1ninutespat which time the intensity of thereaction has abated? The-temperature'is then allowcd'to rise to-200'205--F. andkept' at this rangefor anotherthirtyminutesr At the end of that time'the'exothermie reaction-is over; as shown-by the fact that the mixture starts to coo'l normally.

The-mixture is 'then cooled to-abouP-ISO -F. merely it is sufficiently 'homogenous so "that samples "may b withdrawn foranalysisf This neutral slurry is then pumpe'dihto" a large;'2500 gallon'tank, equipped with a perforated false. bottom fitted with a filter cloth. [The tank iesembles a'verylarge Buckner typefunnel, and like the funnel the space under the perforated false bottom isconnected to a vacuum pump .so that the liquidlabove the" false bottom can be filtered through.. th,e' filtercloth."

Such a reaction as above described gives approximately 900 lbs'. ,dry weightlof acetyleriecdiujr'ea, corresponding toa yieldiof ,approxirnately'72%." Five such reactions are.usually run to give a total of 4500lb's; dry weight of acetylene diurea. The acetylene diurea is fStirred' ith aboutfivetimes its .weight of water, and the water filtered. offa stirring and filtering"is continued until a sample 'of. the acetylene diurea gives a resinous product of the desired lightness .of color. After the final washing and the removal of as much water as possible by filtration,-.the .cake contains approximately 4590 'lbs. dry weight of acetylene .diurea, correspondingeto an over-all y e d o pp qzd at w 2%; I and pprb ms l 0 lbs. of retained water. i i

EXAMPLE C 11 Preparation;ofrthe trimethylol acetylenediurea resinous product To the wet cake above described is added 7700 lbs. of Formalin, which contains 37.5% formaldehyde by Weight. This is in the ratio of three mols of formaldehyde to one mol of acetylene diurea. The mixtureis then stirred until his a thick slurry and NaOH solution added slowly and carefully until the pH is between 9 and10. The amount of NaOH required depends upon the amount of formic acid which is always present in commercial Formalin in small but variable amounts.

A mild exothermic reaction takes place, and the acety lene diurea dissolves to give a light yellow-brown solution of fairly low viscosity. The mixture is stirred until it is certain that all of the acetylene :diurea has dissolved. It is thenhbrought to a pH of 4 or slightly lower, by careful addition of HCl, and. allowed to stand at least twelve hours. Some polymerization takesplace, and the EXAMPLE 2 A combed gingham running 4.5 yards per pound was treated in the same manner as the carded gingham in Example 1 with the formula as follows:

8% of the products of the product produced according to Example C.

2% 2, 2, methylamino propanol hydrochloride-(50% solids).

2.4% a stearamido methyl pyridinium nitrate composition prepared according to Example A.

87.6% water.

viscosity increases until the solution is about as viscous as thin motor oil.

At the end of this time themixture is brought to a pH of 6 to 7 with NaOH, which stops the polymerization. The solutionisfiltered and is ready for use.

For preparing the above acid condensation resinous product, it is desirable to use three mols of formaldehyde to each mol of acetylene diurea, but this ratio may be varied within the range of two to four mols of the former to form the dimethylol and tetramethylol acetylene diureas. 3

EXAMPLE D the methyl ethe rs of trimethylo l Preparation of acetylene diurea To 1 mol of trimethylo1ace tylene diurea, add 218 mls. or 5.5mols of methanol. A clear solution results. 7.0 ml. of concentrated sulfuric acid is then addedwith stirring. In about two hours the etherification is complete, as is shown by complete solubility of the condensation product in methyl alcohol and its partial solubility in acetone. f

The products prepared in the above examples and other materials within the scope of this invention may be used for treating textiles in accordance with the following typical but non-limiting examples;

EXAMPLE 1 1 An aqueous solution was prepared containing the followingingredients: t i

g 10% of the product prodlrced. according to Example C (50% solids). p

2% 2,12, methylamino. propanol hydrochloride, 50%

solids. r

1% of a stearamido methylpyridinium nitrate composition prepared as describedin Example A.

2% corn starch (50%fluidity).

.3% non-ionic wetting agent.

.1% anti-foam.

A pad box was filledwith this solution and a carded cotton gingham fabric running 5.2 yards per pound was padded in a conventional manner with the pad roll pressure Iadjusted to permit a pickup of about 80% padding liquid based on the weight of the fabric. The thus padded fabric was run directly into a tenter frame drying device heated to about 120 C. at a speed suificient to remove the water without curing the resin; The thus treated fabric was passed through a curing oven at 180 rCs f or 70 seconds, at which time the resin was cured.

The anti-foam and the wetting agent are not necessary forall running conditions but were added in the above example to improve commercial operating conditions. The corn starch was added to bodythe fabric and give a C slightly crisper hand, but can be omitted if a softer The gingham produced in accordance with this example was characterized by a beautiful hand characteristic of finest combed goods. The fabric had a very high crease resistance and only a slightly degradation of tear strength.

EXAMPLE 3 The carded gingham fabric of Example 1 was soured with a 0.25% sulphuric acid and rinsed in a non-alkaline water bath to be freed of all residual alkali not exceeding .01% measured as NaOH. 1

The thus soured fabric was treated in the manner set forth in Example 1 with the pad box solution as follows:

20% of the product made according to Example C.

.75 a stearamido methyl pyridinium nitrate composition prepared according to Example A.

79.25% water.

The thus treated fabric showed a crease resistance similar to that of the fabric treated in Example 1 with little difference in the over-all strength properties. The increased amount of resin appears to have made little difference in any of the qualities of the fabric from the fabric of Example 1.

EXAMPLE 4 A neutralized carded. gingham fabric was treated in the manner set forth in Example 1 except that the aqueous pad box solution contained the following:

10% of the product produced according to Example C.

(50% solids.)

2% 2,2,methylamino propanol hydrochloride. 50% solids.

1% octadecyl oxymethyl pyridinium chloride.

The fabric treated in accordance with this example had generally the same properties as the fabric treated in Example 1.

EXAMPLE 5 A neutralized carded gingham fabric was treated in the manner set forth 11 Example 1 except that the aqueous pad box solution contained the following:

generally the same properties as the fabric treated in Example 1.

propanol hydrochloride. 5 0% EXAMPLE 6 A neutralized combed gingham fabric was treated in the manner set forth in Example 1 except. that the aqueous pad box solution contained the following:

10% of the product produced according to Example C.

(50% solids.)

% of the product produced according to Example C.

(50% solids.)

2% 2,2,methylamino propanol hydrochloride.

solids.

1% stearamido methyl pyridinium sulfate.

The fabric treated in accordance with this example had generally the same properties as the fabric treated in accordance with Example 2.

EXAMPLE 8 A neutralized combedgingharn fabric was treated in the manner set forth in Example 1, except that the aqueous pad box solution contained the following:

10% of the product produced according to Example'C.

(50% solids.)

2% 2,2,methylamino propanol hydrochloride. 50%

solids. 1% stearamido methyl beta picolinium nitrate.

The fabric treated in accordance with this example showed the smallest reduction in tear strength per unit of crease-angle recovery improvement of any of the fabrics treated in accordance with the presentinvention.

EXAMPLE 9 A combed gingham fabric was treated in the manner set forth in Example 1 except that the aqueous'pad box solution contained the following:

10% of the product produced according to Example C.

(50% solids.)

2% 2,2,methylainino propanol hydrochloride.

solids.

1% stearamido methyl 'g'amma picolinium nitrate.

The fabric treatedin accordance with this example had generally the. same properties as the fabric treated in accordance with Example 2.

EXAMPLE 10 A neutralized combed gingham fabric was treated in the manner set forth in Example 1 except that the aqueous pad box solution contained the following:

10% of the product produced according to Example C.

(50% solids.)

2% 2,2,methylamino propanol hydrochloride.

solids.

1% stearamido methylol beta gamma picolinium nitrate.

The fabric treated in accordance with this example had generally the same properties as the fabric treated in accordance with Example 2.

EXAMPLE 11 An aqueous solution was prepared containing the following ingredients:

A padbox was filled with this solution and a combed cotton gingham fabric" running? yards per ound was padded in a conventio'nzrl n'ia'nne'r with the pad roll pressureadjustedg to permit av pickup of' about of'the padding. liquid-based on the weight of the fabric. The thus padded fabric was rundirectlyintoa tenterframe drying device heated-to about C;- at-a speed sufficient to remove the water without curing the resin. The thus treated-fabric was passedthrough a-curingoven at 1 80 C. for 70 seconds, at which time the resin was cured.

An aqueous solution was prepared containing. the following ingredients: A

12% dimethylol acetylenediurea. 2% ammonium chloride t 1% ste'aramido methylbeta picolinium nitrate. 3% non-ionic wetting agent. .1-% anti-foam. v

A p'ad' box was filled with this solution and a combed cotton gingham fabric running 4.5 yards per pound was padded in a conventional manner with the pad roll pressure adjusted to permit a pickup of about- 80% of the pad dingliquid based" on the'weight of the fabric. The thus padded fabric was run directly into a t'enter frame drying device heated to about 120 C. at a speed sufficient to remove the water without curing the resin- The thus treated fabric was passed through a curing oven at C. for 70" seconds, at which time the resin was cured.

The fabric treated in accordance with this example had generally the same properties as the fabric treated in accordance with Example 2'.

EXAMPLE 13 An aqueous solution was prepared containing the following ingredients:

10% of the'trimethyl ether of trimethylol acetylene diurea. 2% diamrnoniurn phosphate.

1% stearamido methyl beta picolinium nitrate.

3% non-ionic wetting agent.

1% anti-foam.

A pad box was filled with: this solution and a combed cotton gingham fabric running: 4.5 yards per poundwas padded in a conventional manner with the pad roll pressure adjusted to permit a pickupof about 80% of the padding liquid based-on the weight of the fabric.. The thus padded fabric was run directly intoa tenterframe drying device heated to about 120 C. at a speed suflicientto remove the water without curing the resin. The thus treated fabric was passed through a curing oven at 180 C. for 70*seconds, at which time the'resin was cured. 1

The'fabric treated in accordance with this'example had generally the same properties as the fabric treated in accordance with Example 2'.

EXAMPLE 14 An aqueous solution was prepared containing the following ingredients:

11% of the tri-isopropyl ether of trimethylol acetylene diurea.

2% diethanol amine.

1% steararnido methyl pyridinium nitrate. .3% non-ionic wetting agent.

.1%' anti-foam.

A pad box was filled with'this solution and a combed cotton gin ham fabric runnin 4.5 yards per pound was padded in a conventional manner with the pad'roll ressure adjusted to permit a ickup of about 80% or the adding liqnidrbas'ed on thejweightof thefabric. The thus added'faline was run directly into-a tenterfrarne thus treated fabric was passed through a curing oven at 180 C. for 70 seconds, at which time the resin was cured. The fabric treated in accordance withthis example had generally the same properties as the fabric treated in accordance with Example 2. i

The hand of the fabrics treated in accordance with this invention may be varied by addition of standard fabric finishing agents to the pad box solutions. In general, it has been found that the softening action of the quaternary ammonium catalysts, as defined above,is sufficient for producing a soft hand. Harsher effects can be obtained with such additives as starch,,polyvinyl acetate, etc. q

Permissible modifications and changes in the abovedescribed processes of the present invention are indicated in the appended claims,

1. The process of treatingcellulosic textile, fabric to improve itsjcrease angle; recovery. with a minim um reduction in tear strength per unit of crease angle improvement, which comprises impregnatingsaidfabric with an aqueous solution of a resin forming methylol acetylene diurea and a quaternary ammonium catalysthavingthe formula n A is a connecting linkage selected from the group consisting of an amide, an ester and an ether, the catalyst being capable. of releasing acid only attemperatures in excess of about 130? C., acidifying thefabric to neutralize substantially all residual alkali,drying the fabric at a temperature below 130 C. and heating the fabric to a temperature substantially inexcess of 130 C. to cure the resin forming methylol acetylene diurea, said neutralizationbeing etfectedat sometime prior to the final curing of the resin forming methylol acetylene diurea.

2. The process of treating cellulosic textile fabric to improve its crease angle recoverywith a. minimum reducl tion in tear strength per unit of crease angle recovery improvement, which comprises impregnating said fabric with a water solution of a methylol acetylene diurea and a quaternary ammonium catalyst having the formula:

wherein R1 is the residue of a higher fatty acid having from 14 to 22 carbon atoms, X is the anion of a strong acid, R2 and R3 are hydrogen or a lower alkyl group and A is a connecting linkage selected from the group consisting of an amide, an ester and an ether, drying the thus impregnated fabric and heating the thus dried fabric to cure the methylol acetylene diurea.

3. The process of treating cellulosic textile fabric to improve its crease angle recovery with a minimum reduction in tear strength per unit of crease angle recovery improvement, which comprises impregnating said fabric with a water solution of a methylol acetylene diurea and a quaternary ammonium catalyst having the formula wherein R1 is the residue of a higher fatty acid having from 14 to 22 carbon atoms, X is the anion ofa strong acid, R2 and R3 are hydrogen or a loweralkyl group and A is a connecting linkage selected from the, group consisting of an amide, an ester and an ether, drying the thus impregnated fabric and heating the thus dried fabric to a temperature substantially in excess of C. to cure the methylol acetylene diurea.

4. The process of treating cellulosic textile fabric to improve its crease angle recovery with a minimum reduction in tear strength per unit of crease angle recovery improvement, which comprises impregnating said fabric with a water solution of a methylol acetylene diurea and a stearamido methyl pyridinium nitrate composition containing stearamido methyl pyridinium nitrate with methylol groups, drying the thus impregnated fabric and heating the thus dried fabric to cure the methylol acetylene diurea. 1

5. The process of treating cellulosic textile fabric to improve its crease angle recovery with a minimum reduction in tear strength per unit of crease angle recovery improvement, which comprises impregnating said fabric with a water solution of a methylolacetylene diurea and stearamido methyl beta picolinium nitrate, drying the thus impregnated fabric and heating the thus dried fabric to cure the methylol acetylene diurea. i

6 6. The process of treating cellulosic textile fabric to improve its crease angle recovery with a minimum reduction'in tear strength per unit of crease anglerecovery improvement, which comprises impregnating said fabric with a water solution of a methylol acetylene diurea and a quaternary ammonium catalyst having the formula R1-AC wherein R1 is the residue of a higher fatty acid having from 14 to 22 carbon atoms, X is the onion of a strong acid, R2 and R3 are hydrogen or a lower alkyl group and A is a connecting linkage selected from the group consisting of an amide, an ester and an ether, acidifying the fabric to neutralize all residual alkali substantially in excess of 0.01% measured as sodium hydroxide, drying the thus impregnated fabrieat a temperature which will not decompose said quaternary ammonium catalyst, and heating the thus dried fabric at a temperature which will decompose said quaternary ammonium catalyst to release acid for catalyzing the final setting of said acetylene diurea, said neutralization being effected at some time prior to the final curing of the methylol acetylene diurea.

7. The process of treating cellulosic textile fabric to improve its crease angle recovery with a minimum reduction in tear strength per unit of crease angle recovery improvement, which comprises impregnating said fabric with a water solution of a methylol acetylene diurea and a quaternary ammonium catalyst having the formula wnerein'm is the residue of a higher fattyacid having from Tito ZZ'cJarbo'n' atoms,"X is the anion of a strong acid, R2 and R3 are hydrogen or a lower alkyl group and A is a connecting linkageselected from the group consisting of an amide, an ester and an ether, drying the thus impregnated fabric at a temperature which will not decompose said quaternary ammonium catalyst, heating the thus dried fabric at a temperature which will decompose said quaternary ammonium catalyst to release acid for catalyzing the'final setting of said acetylene diurea derivative', and neutralizing thefab'ric at some time prior to the final curingof [he methylol acetylene diurea.

8, The process of treating celliilosic textile fabric to improve its crease angle recovery with a minimum reduction in'tear strengthper unit of. crease angle recovery improvement, which comprises impregnating said fabric with a water solution of a methylol acetylene diurea and a quaternary ammonium catalyst having the formula pose said quaternary ammonium catalyst and thereby releaseacid for catalyzing the final setting of said acetylene diurea derivative, said neutralization being effected at some time prior to the final curing of the methylol ac'etyten'e; diurea. i

9. The process of treating"cellulosictextile fabric to improve its crease angle recovery with a minimum reduc tion in tear strength per unit of crease angle recovery improvement, which comprises impregnating said fabric with a water solution of a methylol acetylene diurea, 2,2-

methyl amino propanol hydrochloride and a quaternary ammonium catalyst having the formula 12 wherein. R1 is the residue of a higher fatty acid having from 14'to 22carbon atoms, X is the anionof a strong acid, R2 andRa are hydrogen or a lower alkyl groupand A is a connecting linkage selected from thegroup consisting of an amide, an ester and an ether, said 2,2-methyl amino p'r'o'panol hydrochloride being present in the amount required to neutralize the fabric to remove all residual'alkali substantially in excess of 0.01% measured as sodium hydroxide, drying the thus impregnated fabric at a temperaturewhich will not decompose. said quaternary ammoniumca'talyst, heating the thus dried fabric at a temperature which will decompose said quaternary ammonium catalyst and thereby releasing acid for catalyzing the final setting of said methylol acetylene diurea, said neutralization being effected at some time prior to the final curing of the methylol acetylene diurea. V

10. The" process of treating cellulosic textile fabric to improve its crease angle recovery with a minimum reduction in tear strength per unit of crease angle recovery improvement, which comprises the step-wise procedure of first neutralizing the fabric with an acid wash, then impregnating said fabric with a water solution of a methylol acetylene diurea and a quaternary ammonium catalyst having the formula:

H RI

References'Ctted in the file of this patent UNITED STATES PATENTS 2,518,963 Weaver f Aug. 15, 1950 FOREIGN PATENTS France of 1940 

1. THE PROCESS OF TREATING CELLULOSIC TEXTILE FABRIC TO IMPROVE ITS CREASE ANGLE RECOVERY WITH A MINIMUM REDUCTION IN TEAR STRENGTH PER UNIT OF CREASE ANGLE IMPROVEMENT, WHICH COMPRISES IMPREGNATING SAID FABRIC WITH AN AQUEOUS SOLUTION OF A RESIN FORMING METHYLOL ACETYLENE DIUREA AND A QUATERNARY AMMONIUM CATALYST HAVING THE FORMULA 